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At least 253 records · Page 14

Selective oxidation of 3-hydroxypropionic acid to malonic acid over Pd/C: Mechanistic and kinetic study

Malonic acid (MA) is a high-value dicarboxylic acid with strong industrial demand, yet its current production heavily relies on petrochemical feedstocks. Here, we report the first systematic study for sustainable production of MA via oxidation of 3-hydroxypropionic acid (3-HP) with a Pd/Carbon catalyst. The effects of oxidant type (O 2 and H 2 O 2 ), pH, and temperature on the reaction chemistry were comprehensively evaluated. Guided by experimental observation and DFT-calculated thermochemical energetics, reaction networks for 3-HP oxidation with both oxidants are proposed and validated through kinetic modeling. MA was identified as the primary oxidation product, while further oxidation yields acetic acid and oxalic acid. The kinetic model validated the network, displaying excellent agreement (R 2 > 0.95). Kinetic observations also enabled a direct comparison between O 2 and H 2 O 2 and revealed their distinct behaviors. The model was further developed into a temperature-time map, providing insight into conditions that maximize MA production. Malonic acid selectivity of 56.9 % and yield of 50.5 % were achieved at 3 bar oxygen, equimolar NaOH:3-HP ratio, and 50 °C.

3-hydroxypropionic acid↗

Toward UV models of kinetic mixing and portal matter. VI. A more complex dark matter sector?

Portal matter (PM), having both Standard Model (SM) and dark sector charges, can induce kinetic mixing between the 𝑈⁢(1) 𝐷 dark photon and the SM gauge fields at the 1-loop level offering an attractive mechanism by which light (≲1 GeV) thermal dark matter (DM) can interact with visible matter and obtain its observed relic density. In doing so, if the DM is fermionic, the CMB and other astrophysical observations inform us that it must be Majorana/pseudo-Dirac in nature to avoid velocity/temperature-independent 𝑠-wave annihilation to SM final states. How does this idea fit into a more UV-complete picture also including the SM interactions? There are some reasons to believe that at least a first step along this path may not lie too far away in energy due to the renormalization group equations running of the dark gauge coupling, which for a significant range of parameters, becomes nonperturbative at/before the ∼10’s of TeV energy range. This implies that 𝑈⁢(1) 𝐷 must become embedded in an asymptotically free, non-Abelian group, 𝐺 𝐷 , before this can occur. The breaking of this larger group then produces the masses for the PM and the additional gauge fields associated with 𝐺 𝐷 then can lead to new interactions between the SM and the dark sector. Following several bottom-up approaches, we have examined a set of distinctive and testable phenomenological features associated with this general setup, based upon a number of simplifying assumptions. Clearly, it behooves us to explore the impact of these specific assumptions on these predictions for the array of possible experimental tests of this class of models. In most past analyses it has been assumed that DM is a vectorlike, complex singlet under the group 𝐺 𝐷 . If this assumption is relaxed, the dark sector must be augmented by additional fermion(s) and the associated scalar fields needed to break the gauge symmetries while generating the needed Majorana-like mass terms for the DM. In this paper, we analyze the simplest extension of this kind wherein the DM lies in a vectorlike doublet of 𝐺 𝐷 , which we take to have the structure 𝑆⁢𝑈⁢(2) 𝐼 ×𝑈⁢(1) 𝑌 𝐼 as in earlier work, leading to new phenomenological implications. We find, for example, that given the current LHC search constraints on the masses of heavy gauge bosons, the production of these new dark states with large rates is unlikely to occur at colliders unless they are produced singly in 𝑔⁡𝑔 fusion or their pair production cross sections are resonantly enhanced. Here, we also find that an additional mechanism arises to generate hierarchal neutrino masses in such a setup.

Extensions of Higgs sector↗

Final Report for Tech-X Corporations’s contribution to Enhancing Understanding of High Energy Density Plasmas from Wire Array and Solid Liner Implosions Using Fluid Modeling with Kinetic Closures

Recent results from experiments and simulation of magnetically driven pulsed power liners have explored the role of the early-time electrothermal instability in the evolution of the magneto-Rayleigh-Taylor instability. Our focus will be on understanding the development of such instabilities and the potential stabilization mechanisms via electron thermal conduction, viscosity, and large magnetic fields which we expect could play a significant role in supporting the success of the MagLIF program. Experiments have shown that studies of high-energy density plasmas from wire-array implosions require physics modeling that goes well beyond simple models such as ideal magnetohydrodynamics. The goal of this work is to provide increased understanding of these experiments by employing simulations with a multi-fluid extended-MHD model which uses kinetic closures for thermal conduction, resistivity and viscosity. We will use codes easily available to the wider research community, including university students, with a secondary goal of providing the community with well-benchmarked tools capable of advanced modeling of high-energy-density plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Corrosion of 316 L stainless steel under the natural circulation of molten NaCl-MgCl 2 salt

The corrosion behavior of 316 L stainless steel (SS) was studied via the natural circulation of molten eutectic NaCl-MgCl 2 salt through a microloop. The post-corrosion tested 316 L SS microloop sections were characterized with microscopy techniques to determine the microstructural and microchemical changes that occurred at the alloy/salt interface. It was found that 316 L SS showed heterogeneous dissolution at the hot-leg, whereas deposition of corrosion products occurred at the cold-leg. For the first time, experimentally obtained molten salt flow-induced corrosion of 316 L SS results were combined with computational thermodynamic-kinetic models to validate the dissolution and deposition in terms of elemental compositional changes at the alloy/salt interface. The thermodynamic-kinetic modeling predicted that the heterogeneous dissolution of Cr and Fe from the hot-leg section of 316 L SS persisted throughout the salt circulation. The model also estimated that, despite Cr deposition starting earlier than Fe, the total redeposition of Fe is expected to be significantly greater than that of Cr over the circulation of salt. Furthermore, the modeling accurately predicted the subsurface enrichment of Mo which is attributed to the reduced Cr activity and the relatively higher diffusion rate of Mo within the alloy matrix. Here, the agreement between modeling and experimental results confirms that Fe chlorides dissolve at the hot-leg and subsequently deposit at the cold-leg due to activity changes driven by the thermal gradient. By contrast, Cr was not detected in the cold-leg deposits, which is attributed to its weaker temperature dependence on activity, limiting its redeposition under these conditions.

36 - MATERIALS SCIENCE↗

Insight into premixed diethoxymethane flames: Laminar burning velocities, temperatures, and emissions behaviour

Diethoxymethane ((CH 3 CH 2 O) 2 CH 2 , DEM) is a promising carbon-neutral fuel. DEM is a diether or acetal with a molecular structure similar to oxymethylene ethers (CH 3 O–(CH 2 O)n–CH 3 , OME n ). Thus, DEM can be expected to have a similar combustion behavior to OMEs, reducing harmful emissions such as NO x and particulate matter (PM) in internal combustion engines. From both experimental and kinetic modeling, fundamental studies on DEM are scarce in the literature. More studies are required to gain a detailed insight into the oxidation kinetics of DEM. Laminar burning velocity (LBV) is a critical property that allows a detailed assessment of the potential application of DEM in combustion devices. Unfortunately, the literature on the LBV of DEM is limited. Therefore, in this study we have investigated the LBV of DEM using two reactors for the first time, namely a heat flux burner and a combustion chamber. The experimental data is reported for equivalence ratio between 0.7 and 1.7, initial temperatures of 368–423 K, and initial pressure of 1–5 bar. In addition, we developed a detailed kinetic model extending our recent work of Shrestha et al. (Combust. Flame. 246 (2022) 112,426) to characterize the combustion behavior of DEM utilizing the new experimental data from this work and the literature data. Our model performs remarkably well in capturing the newly measured LBV experimental data over various experimental conditions. We found that DEM and dimethoxy methane (DMM) have similar values of LBVs (within ±1.5 cm/s) for a given condition, which indicates that intermediate chemistry governs the flame chemistry. Despite DEM being a larger molecule that is expected to have slightly lower LBVs than DMM, its effect on the measured values of LBVs is negligible. Finally, we experimentally measured NO x formation in DEM flame for the first time. The stochiometric flame has the highest NO x formation. The proposed model predicted the equivalence ratio dependence of NO x nicely. However, it overestimates the NO x formation for stoichiometric DEM/air mixtures by ~30 %. The model suggests that the thermal NO formation route is favored at lean and stochiometric conditions. In contrast, the prompt NO formation route is enhanced for rich mixtures.

10 SYNTHETIC FUELS↗

Fuel Flow Modeling under Thermal Fluidics Considerations within Operational Domains of Molten Salt Reactors

Molten Salt Reactors (MSRs) offer significant versatility supported by their design flexibility and safety advantages due to high temperatures, design customization capabilities, strong negative reactivity feedback effects, and salt chemistry characteristics. Different control schedules and different mass flow rates in the MSR primary systems impact neutronics and thermal hydraulics coupling. The result is two-fold. First, it leads to adaptability in various applications when the customization of a MSR unit is desired. Second, it calls for the quantification of dynamics and safety characteristics to assess the operational domain and make sure reactor stability and inherent safety characteristics are maintained. This paper provides an in-depth transient analysis of the operational implications of MSRs having heat-generating fuel and heat-transporting salt mixed forming liquid fuel salts contained within primary systems. A coupling model was developed to simulate fuel flow in molten salt reactors. A zero-dimensional reactor kinetics model was used with a one-dimensional heat transfer model in the reactor core. The temperature reactivity feedbacks of the fuel salt resulting from the thermal-hydraulics model were used in the reactor kinetics model to complete the coupled code. The model was applied to simulate the Molten Salt Breeder Reactor (MSBR) response at steady state and transients. The developed model was shown to be a suitable tool for the dynamic analysis of molten salt reactors.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

A Theoretical Study of NH 2 Radical Reactions with Propane and Its Kinetic Implications in NH 3 -Propane Blends’ Oxidation

The reaction of NH 2 radicals with C 3 H 8 is crucial for understanding the combustion behavior of NH 3 /C 3 H 8 blends. In this study, we investigated the temperature dependence of the rate coefficients for the hydrogen abstraction reactions of C 3 H 8 by NH 2 radicals using high-level theoretical approaches. The potential energy surface was constructed at the CCSD(T)/cc-pV(T, Q)//M06-2X/aug-cc-pVTZ level of theory, and the rate coefficients were computed using conventional transition state theory, incorporating the corrections for quantum tunneling and hindered internal rotors (HIR). The computed rate coefficients showed a strong curvature in the Arrhenius behavior, capturing the experimental literature data well at low temperatures. However, at T > 1500 K, the theory severely overpredicted the experimental data. The available theoretical studies did not align with the experiment at high temperatures, and the possible reasons for this discrepancy are discussed. At 300 K, the reaction of NH 2 with C 3 H 8 predominantly occurs at the secondary C-H site, which accounts for approximately 95% of the total reaction flux. However, the hydrogen abstraction reaction at the primary C-H site becomes the dominant reaction above 1700 K. A composite kinetic model was built, which incorporated the computed rate coefficients for NH 2 + C 3 H 8 reactions. The importance of NH 2 + C 3 H 8 reactions in predicting the combustion behavior of NH 3 /C 3 H 8 blends was demonstrated by kinetic modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Oxidation and pyrolysis of methyl propyl ether

The ignition, oxidation, and pyrolysis chemistry of methyl propyl ether (MPE) was probed experimentally at several different conditions, and a comprehensive chemical kinetic model was constructed to help understand the observations, with many of the key parameters computed using quantum chemistry and transition state theory. Experiments were carried out in a shock tube measuring time variation of CO concentrations, in a flow tube measuring product concentrations, and in a rapid compression machine (RCM) measuring ignition delay times. The detailed reaction mechanism was constructed using the Reaction Mechanism Generator software. Sensitivity and flux analyses were used to identify key rate and thermochemical parameters, which were then computed using quantum chemistry to improve the mechanism. Validation of the final model against the 1-20 bar 600-1500 K experimental data is presented with a discussion of the kinetics. The model is in excellent agreement with most of the shock tube and RCM data. Strong non-monotonic variation in conversion and product distribution is observed in the flow-tube experiments as the temperature is increased, and unusually strong pressure dependence and significant heat release during the compression stroke is observed in the RCM experiments. These observations are largely explained by a close competition between radical decomposition and addition to O2 at different sites in MPE; this causes small shifts in conditions to lead to big shifts in the dominant reaction pathways. The validated mechanism was used to study the chemistry occurring during ignition in a diesel engine, simulated using Ignition Quality Test (IQT) conditions. At the IQT conditions, where the MPE concentration is higher, bimolecular reactions of peroxy radicals are much more important than in the RCM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transport Modeling of Kinetically Limited Microscale Extraction Systems: Droplet and Supported Liquid Membrane Separations

Microfluidic droplet extraction devices can be used to efficiently measure solute phase transfer kinetics in liquid–liquid extraction systems. In this work, a droplet extraction apparatus was constructed using off-the-shelf and custom 3D printed parts for less than 110 USD. The interfacial kinetics of the transfer of Pu(IV) between an aqueous nitric acid phase and a 5 v/v% tridodecylamine (TDA) in toluene phase were characterized by determining the extent of Pu(IV) transfer between phases at different flow rates. Forward interfacial rate constants calculated from this data using an analytical model are 5.6 × 10 –3 mm s –1 under extraction (aqueous-to-organic solute transfer) conditions and 3.3 × 10 –3 mm s –1 under stripping (organic-to-aqueous solute transfer) conditions. The analytical model is valid when the rate of solute transfer across the interface between the two liquid phases has pseudo-first-order reversible reaction kinetics and is slow relative to the rate of solute transport to the interface. The change in the outlet concentration with residence time determined using the analytical model was compared with the results of a numerical model accounting for advection/diffusion to the interface in addition to kinetically limited interfacial solute transfer. These calculations revealed that for systems with forward interfacial rate constants greater than approximately 10 –2 mm s –1 , the analytical model must be supplemented with a numerical transport model accounting for an additional advection/diffusion mass transfer resistance. This threshold corresponds to a Damköhler number of one. The measured interfacial kinetic rate constants for Pu(IV)/TDA were used in a supported liquid membrane (SLM) numerical model, which showed that the Pu(IV) phase transfer kinetics are fast enough for use in a practical separation.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Automated identification and calculation of prompt effects in kinetic mechanisms using statistical models

The kinetics of prompt dissociation involves rovibrationally excited species (generally formed by exothermic reactions) which may dissociate or isomerize prior to thermalization via collisions with the bath gas. Treating such rovibrationally excited species (so-called "hot" species) with standard kinetic phenomenology may result in incorrect macroscopic representation of their reactivity. Here this work presents the first fully automated methodology for the calculation of prompt effects of a chosen species in a kinetic mechanism, including (i) reaction selection; (ii) theoretical calculation of rate constants and prompt branching fractions; and (iii) final rate constant fitting. The energy partition between hot fragments is estimated using a variety of statistical models, including a new physically sound microcanonical statistical model based on the rovibrational density of states of the fragments. The methodology is validated against literature data for the prompt dissociations of HCO and C 3 H 7 radicals. The microcanonical statistical model is in better agreement with trajectory simulations for larger species and is thus applicable for practical systems that typically involve large molecules, for which direct dynamics calculations are impractical. The automated workflow is applied to the evaluation of the effects of prompt dissociation for two isomeric radicals C 4 H 7 1-3 (1-methylallyl) and C 4 H 7 1-4 (3-buten-1-yl). Twelve H-atom abstraction reactions are selected and the corresponding rate constants are computed with first principles theory. The microcanonical statistical model predicts that prompt dissociations of C 4 H 7 1-3 and C 4 H 7 1-4 are already significant at 1000K, resulting in differences of up to an order of magnitude at 2000K with respect to the phenomenological thermal rate constants. To illustrate the effects of prompt dissociation on simulations of experimental data, the calculated prompt rate constants are implemented in both CRECK and C3MechV3.3 kinetic mechanisms. Simulations of experimental flame data illustrate the noticeable impact of prompt dissociation kinetics on the high-temperature combustion reactivity of C 4 H 8 -1 and C 4 H 8 -2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An E and B gyrokinetic simulation model for kinetic Alfvén waves in tokamak plasmas

The gyrokinetic particle simulation is a powerful tool for studies of transport, nonlinear phenomenon, and energetic particle physics in tokamak plasmas. While most gyrokinetic simulations make use of the scalar and vector potentials, a new model (GK-E&B) has been developed by using the E and B field in a general form and has been implemented in simulating kinetic Alfvén waves in uniform plasma. In our work, the Chen et al. GK-E&B model has been expressed, in general, tokamak geometry using the local orthogonal coordinates and general tokamak coordinates. Its reduction for uniform plasma is verified, and the numerical results show good agreement with the original work. The theoretical dispersion relation and numerical results in the local model in screw pinch geometry are also in excellent agreement. Numerical results show excellent performance in a realistic parameter regime of burning plasmas with high values of β/(M e k$^{2}_{⊥}$ρ$^{2}_{i}$), which is a challenge for traditional methods due to the “cancellation” problem. As one application, the GK-E&B model is implemented with kinetic electrons in the local single flux surface limit. With the matched International Tokamak Physics Activity-Toroidicity-induced Alfvén Eigenmodes parameters adopted, numerical results show the capability of the GK-E&B in treating the parallel electron Landau damping for realistic tokamak plasma parameters. As another application, the global GK-E&B model has been implemented with the dominant electron contribution in the cold electron limit. Its capability in simulating the finite E || due to the finite electron mass is demonstrated.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Explosive Soot Challenge (Final Report)

This project assembled a broad ensemble of modeling and experimentation tools to study the morphological and optical properties of detonation soots in explosive fireballs. A gram-scale hemispherical high explosive was studied in a low-pressure controlled environment using in-situ experimentation with diffusely illuminated visible absorption spectroscopy, particle sizing through light scattering techniques, and post-test collections with subsequent morphological analysis. Hydrocode modeling was performed to replicate the detonation flow observations, and subsequent aerosol kinetics models provided particle size distributions and extinction coefficients from the hydrocode results. Experimentally observed soot morphologies agreed with expectation from the literature - a bimodal distribution was found, brought upon by the particles growing to a size where their inertia and fluid wakes are non-negligible. The aerosol kinetics model did not replicate the observed bimodal size distribution for lack of a coagulation kernel to represent the behavior. To recover particulate optical properties, a spectrally resolved absorption spectroscopy method termed Spectral diffuse back-illuminated extinction imaging (SBI-EI) was developed and implemented on two explosive types. Inverting the absorption spectra using a Kramers-Kronig consistent method yielded the complex index of refraction for the soots produced by the explosives. This method resulted in an unrealistic index of refraction for one of the two explosives, and this is suspected to be due to the model neglecting scattering brought upon by the large particle sizes observed. In addition to the core work, three additional studies were performed in parallel. These investigated the impact of scattering on diffuse absorption spectroscopy, studied how soots oxidate and sublimate in a well-controlled shock tube, and laid the theoretical groundwork for a new collision kernel to replicate the bimodal size distribution from the observations. Summaries of these efforts are included at the end of this report.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Data for Selective Oxidation of 3-Hydroxypropionic Acid to Malonic Acid over Pd/C: Mechanistic and Kinetic Study

Malonic acid (MA) is a high-value dicarboxylic acid with strong industrial demand, yet its current production heavily relies on petrochemical feedstocks. Here, we report the first systematic study for the sustainable production of MA via oxidation of 3-hydroxypropionic acid (3-HP) with a Pd/Carbon catalyst. The effects of oxidant type (O2 and H2O2), pH, and temperature on the reaction chemistry were comprehensively evaluated. Guided by experimental observation and DFT-calculated thermochemical energetics, reaction networks for 3-HP oxidation with both oxidants are proposed and validated through kinetic modeling. MA was identified as the primary oxidation product, while further oxidation yields acetic acid and oxalic acid. The kinetic model validated the network, displaying excellent agreement (R2 > 0.95). Kinetic observations also enabled a direct comparison between O2 and H2O2 and revealed their distinct behaviors. The model was further developed into a temperature-time map, providing insight into conditions that maximize MA production. Malonic acid selectivity of 56.9 % and yield of 50.5 % were achieved at 3 bar oxygen, equimolar NaOH:3-HP ratio, and 50 °C.

Bioproducts↗

Application of NEAMS Codes to Capture MSR Phenomena

This report documents work completed in FY21 under the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program’s Molten Salt Reactor (MSR) Application Drivers activity at Argonne. The common focus was on identifying the modeling and simulation functional requirements for designing, licensing, and operating MSRs and applying those capabilities already developed in NEAMS tools to example problems of interest. The four main parts of this report each focuses on a specific area of simulation physics as it relates to MSR phenomena: fuel evolution, chemistry, computational fluid dynamics (CFD), and systems analysis. In terms of fuel evolution, which includes depletion, decay, on-line separations, and transmutation, the current state of computational capabilities for modeling this behavior in liquid-fueled molten salt reactor is discussed. Some of the functional requirements to accomplish the various applications of MSR fuel depletion modeling are highlighted, followed by a summary of recent approaches and code development activities. The chemistry functional requirements were discussed in the context of several applications of high importance for MSRs, such as corrosion, salt chemistry, and species transport. Each of these types of chemistry modeling have considerable impact on various aspects of reactor applications, including informing on reactor designs, improving operational efficiencies, analyzing safety and reactivity concerns, and estimating the mechanistic source term of the reactor. A brief overview is also provided on code development activities ongoing under NEAMS relevant to chemistry modeling of MSRs. In terms of CFD applications, the state-of-the-art spectral element code, Nek5000 was used to model the fluid dynamics within a full core of the Molten Salt Fast Reactor (MSFR) concept designed as part of the Euratom EVOL project. This concept was selected as the challenge problem because of its similar features to several U.S. industry concepts. The goal was to model some of the fast MSR design challenges, including potential large internal re-circulations, the need of accurate tracking of delayed neutron precursors (DNP), and the lack of relevant thermal-hydraulics models/correlations, etc. Therefore, a series of CFD models were created for the MSFR core cavity using a k – τ model two-equation model for the turbulence. These first full core results demonstrated that any potential recirculation zones could be properly identified with the current NEAMS CFD capabilities. The development of these models will also set the stage for future testing of Nek5000’s functionalities to model other MSR thermal-fluid phenomena. Lastly, the validation of SAM against experimental data from the Molten Salt Reactor Experiment, which started in FY19, continues with the inclusion of modeling the reactivity insertion tests. This involved using SAM and its point kinetics model for flowing fuel salt to recreate the time dependent power changes and response after positive reactivity insertions at the 1, 5, and 8 MWt power levels. Through these exercises, several code modifications were suggested to the SAM development team and accommodated to enable closer agreement with solid technical and physical justifications. These include adding a moderator reactivity feedback coefficient as an available input and modifying the solution approach for the point kinetics model. Additional SAM development suggestions for flowing fuel MSRs include adding the capability to allow the moderator power change proportionally with the reactor power and enabling specification of the power and DNP distributions separately.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Uncertainty Quantification and Error Propagation in the Enthalpy and Entropy of Surface Reactions Arising from a Single DFT Functional

Accounting for parametric uncertainty in models is essential for quantifying the models’ predictive ability. Recently, approaches have been introduced to estimate parametric uncertainty in kinetic models while accounting for correlations among energy parameters. However, correlations have been estimated indirectly and correlations in entropies have not been accounted for. For surface-catalyzed microkinetic models of >C2 (more than two carbon-containing) molecules, which consist of thousands of reaction steps and intermediate surface species, first-principles density functional theory (DFT) is costly, and thus, estimation of thermochemistry and reaction barriers requires surrogate methods of DFT, such as group additivity and Brønsted–Evans–Polanyi relationships, respectively. For such parametrization, model uncertainty is unclear. This work develops a framework to overcome these gaps using group additivity and a single DFT functional. We estimate correlations in parameters of kinetic models and quantify uncertainty for thermochemistry, reaction barriers, reaction paths, and ultimately reaction rates, accounting also for the contribution of entropic uncertainty. Furthermore, the approach is illustrated on propane combustion and ethane oxidative dehydrogenation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Compositional patterning in irradiated alloys: Effective potentials and effective interfacial energy

Compositional patterning (CP) in binary alloys during energetic particle irradiation is studied using a kinetic model that considers two competing kinetic processes, a thermally activated one promoting macroscopic phase separation (MPS) of the concentration field c(r,t) and a forced one resulting in finite-range random atomic mixing. The forced mixing is modeled by a Gaussian relocation distribution with a characteristic distance R. A series of approximate kinetic models are introduced by expanding the mixing function into a series of n terms, thus replacing the non-local evaluations of the concentration field c(r'-r,t) by local derivatives of c(r,t). This approach makes it possible to obtain exact effective potentials and build steady-state diagrams for each order-n model. Phase field (PF) simulations using these order-n models reveal that near the onset of patterning, phase evolution is accurately described using an order-3 model, which changes smoothly from an extended Cahn-Hilliard free energy in the MPS regime to a one-mode Swift-Hohenberg functional in the CP regime. Deeper into the patterning regime, higher-order models are required to achieve convergence, yielding square-like concentration profiles characteristic of a strong segregation regime. These higher-order effective free energies are analogous to multimodal Swift-Hohenberg functionals. Here, a new definition for the effective interfacial energy is proposed in the CP regime, since the interfacial area is no longer an excess quantity in that regime, precluding the use of the standard thermodynamic definition of interfacial energy.

36 MATERIALS SCIENCE↗

Investigating Kinetic Mechanisms of Soot Formation in Plasma Pyrolysis of Methane via Active Learning (Final Technical Report)

Plasma pyrolysis of methane is an effective route for zero-carbon hydrogen production. Yet, soot generated from pyrolysis of hydrocarbons is detrimental to the climate and human health. There is ample experimental and theoretical evidence that suggests polycyclic aromatic hydrocarbons (PAHs) are the molecular precursors to soot particles. The reaction pathways of PAH formation are intricately dependent on a multitude of process parameters, whose kinetic mechanisms are not well-understood in plasma pyrolysis. This project aims to leverage advances in the kinetic modeling of soot formation in combustion, as well as in surrogate modeling and active learning, to systematically investigate the effects of process parameter on the kinetics of PAH formation in plasma pyrolysis of methane. To this end, we propose to use the PAH formation kinetics model developed by the PPPL/PU group based on the well-established ABF and HACA mechanisms, coupled with low-temperature plasma models. We will develop an active learning (AL) framework based on Bayesian optimization to systematically and data-efficiently explore the complex and multivariable parameter space of plasma pyrolysis in order to quantify the effects of plasma and feed parameters on the ABF and HACA kinetic pathways. AL is the branch of machine learning concerned with systematically querying samples from a system (experimental or computational) to train a data-driven model that maps design parameters to a performance criterion. We will use the data generated via AL to perform global sensitivity analysis, combined with uncertainty quantification, to elucidate the impact of different reaction pathways on minimizing formation of soot precursors. This study will result in an improved understanding of kinetics of PAH formation in plasma pyrolysis and can pave the way for more advanced mechanistic studies (e.g., soot nucleation mechanisms). Additionally, the findings will be useful for establishing practical strategies for increasing the pyrolysis efficiency and producing high-grade carbon for synthesis of nanomaterials.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Vertical effective stress and temperature as controls of quartz cementation in sandstones: Evidence from North Sea Fulmar and Gulf of Mexico Wilcox sandstones

Here we present quantitative petrographic data, high spatial resolution oxygen isotope analyses of quartz cement, basin modelling and a kinetic model for quartz precipitation for two Paleocene-Eocene Wilcox Group sandstones from Texas and two Jurassic Fulmar Formation sandstones from the Central North Sea. At each location, one sandstone has been buried to ca. 145 °C and one to ca. 185 °C. A key difference between the Wilcox and Fulmar burial histories is that the Wilcox sandstones are currently at higher vertical effective stresses and, from basin modelling studies, have been subjected to generally higher vertical effective stresses through their burial history. The amounts of quartz cement in the Wilcox sandstones are between 12 and 18%, and between 2 and 6% in the Fulmar sandstones. High-spatial-resolution oxygen isotope data obtained from the quartz cements suggest temperature ranges for quartz precipitation from 60 to 80 °C to values approaching maximum burial temperature. Factors such as grain coatings or the timing of petroleum emplacement cannot explain the differences in the amounts of quartz cement. Petrographic data show that most of the silica for quartz cement can be derived from intergranular pressure dissolution. Although the sample set is small, we interpret the results to suggest that the differences in quartz cementation in Fulmar and Wilcox sandstones can be explained better by differences in their vertical effective stress history than their temperature history; in this case, the supply of silica rather than the precipitation of quartz becomes an important control on the rate and extent of cementation.

58 GEOSCIENCES↗